CN100481285C - 固体电解电容器的制造方法 - Google Patents
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Abstract
本发明提供一种固体电解电容器的制造方法,包括:将作为氧化剂的烷氧基苯磺酸金属盐或烷基磺酸金属盐,与导电性高分子材料一同混合到溶剂中的工序;在该混合溶剂内浸渍电容器元件(2),并通过热聚合反应,在电容器元件(2)内形成导电性高分子层的工序。
Description
技术领域
本发明涉及一种卷绕阳极箔和阴极箔的固体电解电容器的制造方法。
背景技术
图2是以往的固体电解电容器1的断面主视图,图1是以往的电容器元件2的立体图(例如,参照日本专利公告公报平4—19695号)。
在上面开口的铝制的壳体3内,收纳电容器元件2,用橡胶制的填充部件30密封壳体3的开口。卷曲壳体3的上端部,固定填充部件30,并在壳体3的上面,安装塑料制的座板31。从电容器元件2延伸的引线21、21贯通填充部件30及座板31后,横向弯曲。
如图1所示,电容器元件2由以下方式构成,即,将作为形成有电介质氧化覆膜的铝箔的阳极箔4以及作为铝箔的阴极箔5,介于作为纸等绝缘体的隔板6滚筒状卷绕。在电容器元件2的内部,形成导电性高分子层。从阳极箔4和阴极箔5,引出一对引线板25、25,并从该引线板25、25,延伸出上述引线21、21。
以下,说明在电容器元件2内形成导电性高分子层的顺序。首先,在乙醇溶剂中溶解高分子材料噻吩的同时,添加金属盐等氧化剂,并将电容器元件2浸渍在溶剂内。在室温——约300℃下产生热聚合反应,在电容器元件2内生成导电性高分子层。
该高分子具有导电性,是因为氧化剂的阴离子作为掺杂剂进入高分子结构内,形成空穴。另外,以聚噻吩作为导电性高分子的固体电解电容器是众所周知的(例如,参照日本专利公开公报平2—15611号),而作为高分子材料,也可以采用吡咯、苯胺。此外,已知还有以聚亚乙二氧基噻吩(polyethylene dioxy-thiophene)作为电解质,氧化剂采用对甲苯磺酸第三铁(这里的第三铁与Fe3O4相对应)的固体电解电容器(例如,参照日本国专利公开公报平9—293639号)。由于聚亚乙二氧基噻吩的聚合反应速度缓慢,因此能在电容器元件2内形成由均匀的导电性高分子构成的电解质层。
对于此种电容器,市场上要求降低ESR(等效串联电阻)。以往虽能使用了以聚亚乙二氧基噻吩作为电解质的电容器,但没能获得满足市场要求的ESR特性。此外认为,由于电容器1的静电容量及寿命试验中的偏差大,所以不能在电容器元件2内部充分致密并且均匀地形成电解质。
发明内容
本发明目的在于提供一种ESR更低的电容器。
本发明提供一种固体电解电容器的制造方法,具有:作为氧化剂,将烷氧基苯磺酸或烷基磺酸的金属盐,与导电性高分子材料一同混合到溶剂中的工序;在该混合溶剂中,浸渍电容器元件2,通过热聚合反应,在电容器元件2内形成导电性高分子层的工序。
附图说明
图1是以往的电容器元件的立体图。
图2是以往的固体电解电容器的断面主视图。
具体实施方式
以下,参照附图,详细说明本发明的一实施例。
固体电解电容器1的整体形状与图2所示的以往形状相同。如图1所示,电容器元件2具有以下结构,即,将作为形成有化成覆膜的铝箔的阳极箔4、与作为铝箔的阴极箔5,介于作为绝缘体的隔板6滚状卷绕,再用带子26固定。在电容器元件2的内部形成导电性高分子层。关于导电性高分子,有聚噻吩、聚吡咯、聚苯胺等,但在本例中举例噻吩系高分子。从电容器元件2引出一对引线21、21。
固体电解电容器1按以下顺序形成。由于阳极箔4从铝制薄板上裁切而成,因此在阳极箔4的端面未形成电介质氧化覆膜。所以,首先进行电容器元件2的切口化成,在阳极箔4的端面形成电介质氧化覆膜。然后,用280℃热处理电容器元件2,使电介质氧化覆膜的特性稳定。
然后,将电容器元件2浸渍在作为稀释剂含有乙醇的3,4—亚乙二氧基噻吩及成为氧化剂的金属盐的混合溶液中。
通过在室温——大约300℃引起热聚合反应,在电容器元件2内形成导电性高分子层,完成电容器元件2。将电容器元件2封入在上述壳体3内,制成固体电解电容器1。
在本例中,其特征在于,作为氧化剂,采用烷氧基(CnH2n+1O—)苯磺酸或烷基(CnH2n+1—)磺酸金属盐。作为烷氧基苯磺酸使用甲氧基苯磺酸,作为烷基磺酸使用甲磺酸。
作为以往例及实施例1、2、3,本申请人采用了不同的氧化剂,各制作了20个电容器元件2。表1示出在以往例及实施例1、2、3中采用的氧化剂。
表1
在表1中,作为以往例,以对甲苯磺酸铁作为氧化剂,制作了电容器元件2。然后,作为实施例1,只以甲氧基苯磺酸铁作为氧化剂,制作了电容器元件2。作为实施例2,以对甲苯磺酸铁和甲磺酸铁的混合物作为氧化剂,制作了电容器元件2。作为实施例3,以甲氧基苯磺酸铁和甲磺酸铁的混合物作为氧化剂,制作了电容器元件2。将各电容器元件2装入壳体3内,封口,制成固体电解电容器1。另外,溶剂都是乙醇,导电性高分子是3,4—亚乙二氧基噻吩。
哪一个电容器1都是额定电压4V、静电电容150μF、壳体3的外形尺寸为直径6.3mm、高度6.0mm的电容器。
对实施例及以往例的电容器,外加120Hz的交流额定电压,测定静电电容(Cap,单位:μF),外加100Hz的交流额定电压,测定等效串联电阻(ESR,单位:mΩ)。表2示出测定结果。电的特性值为20个的平均值。
表2
Cap | ESR | |
以往例实施例1实施例2实施例3 | 150152150151 | 20151615 |
如上述表2所示,如果采用本方法制作电容器元件2,就能够在不降低静电电容的情况下改善ESR特性。
作为该改善的理由,认为如下。与作为氧化剂只采用如甲苯磺酸这样的芳香族磺酸金属盐相比,通过采用甲氧基苯磺酸这样的烷氧基苯磺酸金属盐或甲磺酸这样的烷基磺酸金属盐与芳香族磺酸金属盐的混合物,可以提高氧化剂溶液的酸度。结果,氧化剂的阴离子容易作为掺杂剂进入到高分子结构内,导电性高分子的聚合效果提高,从而认为提高了电容器元件2内的导电性高分子的填充率。
另外,作为烷氧基苯磺酸,不仅可以使用甲氧基苯磺酸,还可以使用乙氧基苯磺酸、丁氧基苯磺酸。另外,作为烷基磺酸,不仅有甲磺酸,还有乙磺酸、丙磺酸、丁磺酸。一般,如果采用分子量大的酸而形成电容器元件2,则有耐热性、热稳定性提高,特性稳定的倾向。
此外,在构成金属盐的过渡金属不仅可以是3价铁,还可以是铜、铬、铈、锰、锌。
在本例中,是通过卷绕阳极箔4和阴极箔5而构成了电容器元件2,但也可以由阀金属的烧结体或板材的叠层结构构成电容器元件2。在这里,所谓阀金属,是在表面上形成氧化覆膜的金属,适合采用铝、钽、铌等。此外,壳体3的上面开口,也可以用环氧树脂堵塞。另外,电容器的形状,也可以是径向引线式。
在本发明的固体电解电容器中,作为氧化剂,采用烷氧基苯磺酸或烷基磺酸金属盐,从而能够在不降低静电电容的情况下改善ESR。
作为该改善的理由,认为如下。与作为氧化剂只采用甲苯磺酸这样的芳香族磺酸金属盐相比,通过采用甲氧基苯磺酸这样的烷氧基苯磺酸金属盐或甲磺酸这样的烷基磺酸金属盐与芳香族磺酸金属盐的混合物,可提高氧化剂溶液的酸度。结果,氧化剂的阴离子作为掺杂剂容易进入到高分子结构内,导电性高分子的聚合效果提高,从而认为提高了电容器元件2内的导电性高分子的填充率。可能就因为这样,在电容器元件2内部十分致密且均匀地形成了电解质。
Claims (3)
1.一种固体电解电容器的制造方法,是具有在阳极侧形成电介质氧化覆膜,同时在内部形成有导电性高分子层的电容器元件(2)的固体电解电容器的制造方法,包括:
将作为氧化剂的烷氧基苯磺酸金属盐和/或烷基磺酸金属盐,与导电性高分子材料一同混合到溶剂中的工序;
在该混合溶液内浸渍电容器元件(2),并通过热聚合反应,在电容器元件(2)内形成导电性高分子层的工序。
2.如权利要求1所述的固体电解电容器的制造方法,其特征是:
构成金属盐的过渡金属是3价铁、铜、铬、铈、锰、锌中的任何一种。
3.如权利要求1所述的固体电解电容器的制造方法,其特征是:
作为氧化剂,使用从烷氧基苯磺酸金属盐和烷基磺酸金属盐中分别选择一种以上,并混合该2种以上的金属盐。
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JP2008205405A (ja) * | 2007-02-22 | 2008-09-04 | Sanyo Electric Co Ltd | 固体電解コンデンサの製造方法 |
JP4342607B2 (ja) | 2007-06-26 | 2009-10-14 | テイカ株式会社 | 導電性高分子合成用酸化剤兼ドーパント、そのアルコール溶液、導電性高分子および固体電解コンデンサ |
JP4916416B2 (ja) * | 2007-10-30 | 2012-04-11 | サン電子工業株式会社 | 電解コンデンサの製造方法及び電解コンデンサ |
CN101932653B (zh) | 2008-04-21 | 2013-02-27 | 帝化株式会社 | 导电性组合物的分散液、导电性组合物以及固体电解电容器 |
CN101350252B (zh) * | 2008-09-17 | 2012-06-27 | 中国振华(集团)新云电子元器件有限责任公司 | 一种常温稳定存放的导电高分子电解质聚合液配方及其应用 |
WO2010065859A2 (en) * | 2008-12-04 | 2010-06-10 | Lumimove, Inc., D/B/A Crosslink | Intrinsically conductive polymers |
WO2011068026A1 (ja) | 2009-12-04 | 2011-06-09 | テイカ株式会社 | 導電性高分子およびそれを固体電解質として用いた固体電解コンデンサ |
US8684576B2 (en) | 2009-12-18 | 2014-04-01 | Tayca Corporation | Solid electrolytic capacitor |
EP2479201B1 (en) | 2010-08-19 | 2015-09-02 | Tayca Corporation | Oxidant/dopant solution for producing conductive polymer, conductive polymer and solid electrolytic capacitor |
US8848342B2 (en) | 2010-11-29 | 2014-09-30 | Avx Corporation | Multi-layered conductive polymer coatings for use in high voltage solid electrolytic capacitors |
WO2012153790A1 (ja) | 2011-05-12 | 2012-11-15 | テイカ株式会社 | 固体電解コンデンサの製造方法 |
CN103748164B (zh) | 2011-09-06 | 2016-09-14 | 帝化株式会社 | 导电性高分子分散液、导电性高分子及其用途 |
WO2013094462A1 (ja) | 2011-12-19 | 2013-06-27 | テイカ株式会社 | 電解コンデンサおよびその製造方法 |
US9076592B2 (en) | 2012-03-16 | 2015-07-07 | Avx Corporation | Wet capacitor cathode containing a conductive coating formed anodic electrochemical polymerization of a microemulsion |
US9053861B2 (en) | 2012-03-16 | 2015-06-09 | Avx Corporation | Wet capacitor cathode containing a conductive coating formed anodic electrochemical polymerization of a colloidal suspension |
US8971020B2 (en) | 2012-03-16 | 2015-03-03 | Avx Corporation | Wet capacitor cathode containing a conductive copolymer |
JP5725637B1 (ja) | 2013-09-11 | 2015-05-27 | テイカ株式会社 | 導電性高分子製造用モノマー液およびそれを用いる電解コンデンサの製造方法 |
US9165718B2 (en) | 2013-09-16 | 2015-10-20 | Avx Corporation | Wet electrolytic capacitor containing a hydrogen protection layer |
US10403444B2 (en) | 2013-09-16 | 2019-09-03 | Avx Corporation | Wet electrolytic capacitor containing a composite coating |
US9183991B2 (en) | 2013-09-16 | 2015-11-10 | Avx Corporation | Electro-polymerized coating for a wet electrolytic capacitor |
JP5788127B1 (ja) | 2014-02-27 | 2015-09-30 | テイカ株式会社 | 導電性高分子製造用酸化剤兼ドーパント、その溶液、それらのいずれかを用いて製造した導電性高分子およびその導電性高分子を電解質として用いた電解コンデンサ |
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